Hi there,
Marketo DOES NOT dedupe leads that originate in SFDC.
The initial sync loads data into Marketo. If a lead comes into Marketo (import, form, etc) and it matches by EMAIL, then the lead will be merged with an existing lead.
You have to use a dupe blocker in SFDC to block new leads there.
So in your example, you have
SFDC: Jane creates joe@company.com
Marketo: Joe creates joe@company.com <--this is merged with the record in SFDC
If you had the opposite
SFDC: joe@company.com x 2
Marketo sees joe@company.com x 2
if Joe then came into Marketo, Marketo will choose the most recent record to merge. You'll still have 2 records though.